WO2011052666A1 - フッ化ビニリデン系重合体粉末およびフッ化ビニリデン系重合体溶液 - Google Patents

フッ化ビニリデン系重合体粉末およびフッ化ビニリデン系重合体溶液 Download PDF

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WO2011052666A1
WO2011052666A1 PCT/JP2010/069131 JP2010069131W WO2011052666A1 WO 2011052666 A1 WO2011052666 A1 WO 2011052666A1 JP 2010069131 W JP2010069131 W JP 2010069131W WO 2011052666 A1 WO2011052666 A1 WO 2011052666A1
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vinylidene fluoride
fluoride polymer
polymer powder
temperature
pyrrolidone
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PCT/JP2010/069131
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English (en)
French (fr)
Japanese (ja)
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民人 五十嵐
宏 坂部
絵美 菅原
慎太郎 武藤
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株式会社クレハ
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Priority to EP10826798.0A priority Critical patent/EP2495265B1/en
Priority to CN201080048629.3A priority patent/CN102597024B/zh
Priority to JP2011538468A priority patent/JP5766120B2/ja
Priority to KR1020127013573A priority patent/KR101409692B1/ko
Priority to US13/503,876 priority patent/US9267016B2/en
Publication of WO2011052666A1 publication Critical patent/WO2011052666A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C08F14/22—Vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to a vinylidene fluoride polymer powder and a vinylidene fluoride polymer solution. More specifically, a vinylidene fluoride polymer powder excellent in solubility in an aprotic polar solvent such as N-methyl-2-pyrrolidone, and a vinylidene fluoride polymer solution obtained from the polymer powder and the aprotic polar solvent About.
  • aprotic polar solvent such as N-methyl-2-pyrrolidone
  • a vinylidene fluoride polymer solution obtained by dissolving vinylidene fluoride polymer powder in N-methyl-2-pyrrolidone (hereinafter also referred to as NMP) is used. in use.
  • Patent Document 1 As a method for dissolving a vinylidene fluoride polymer, a method is known in which a vinylidene fluoride polymer powder is first dispersed in a poor solvent and then stirred and dissolved in a good solvent (for example, Patent Documents). 1).
  • Patent Document 1 it is described that acetone, tetrahydrofuran or the like is used as a poor solvent and NMP or the like is used as a good solvent.
  • Patent Document 1 since it is necessary to disperse the vinylidene fluoride polymer powder in a poor solvent and to stir in a good solvent, the operation is complicated and the productivity tends to be inferior. there were. Moreover, although the aspect which removes a poor solvent from a vinylidene fluoride polymer solution is also described, providing the process of removing a poor solvent causes a high cost.
  • a porous vinylidene fluoride polymer powder is known (for example, see Patent Document 2).
  • the vinylidene fluoride polymer powder described in Patent Document 2 can be obtained by a supercritical suspension polymerization method including a step of suspending a vinylidene fluoride monomer and a step of supercritical polymerization.
  • the vinylidene fluoride polymer powder described in Patent Document 2 does not suppress the formation of maco. Therefore, if the method of dispersing the vinylidene fluoride polymer powder in the solvent is inappropriate, mako is formed. There was a problem that the solubility was lowered.
  • the present invention has been made in view of the above-described problems of the prior art, and is a vinylidene fluoride polymer powder that is more excellent in solubility in an aprotic polar solvent such as NMP than in the prior art, and the powder, aprotic
  • An object of the present invention is to provide a vinylidene fluoride polymer solution obtained from a polar solvent.
  • the vinylidene fluoride polymer powder of the present invention has an N-methyl-2-pyrrolidone permeability of 12 to 100% in the following N-methyl-2-pyrrolidone permeability test.
  • N-methyl-2-pyrrolidone permeability test A glass tube with an inner diameter of 8 mm, which is filled with absorbent cotton at the bottom, is erected vertically, and sea sand with a particle size of 0.1 to 0.3 mm is placed on the absorbent cotton.
  • a lower sea sand layer is formed by filling 1 g of the sea sand so that the surface of the sea sand becomes flat, and 1 g of vinylidene fluoride polymer powder is placed on the surface of the lower sea sand layer and the boundary surface with the lower sea sand layer and the fluoride.
  • a vinylidene fluoride polymer powder layer is formed, and the particle size is increased on the surface of the vinylidene fluoride polymer powder layer.
  • An upper sea sand layer is formed by filling 1 g of 0.1 to 0.3 mm of sea sand so that the boundary surface with the vinylidene fluoride polymer powder layer and the surface of the sea sand become flat.
  • N-methyl-2-pyrrolidone dyed with methylene blue (methylene blue concentration: 0.05 mass%) (liquid temperature 23 ° C.) was injected onto the surface of the upper sea sand layer, and 3 minutes after the injection, The penetration depth of N-methyl-2-pyrrolidone dyed with methylene blue into the vinylidene fluoride polymer powder layer and the thickness of the vinylidene fluoride polymer powder layer were measured, and the penetration depth was determined based on the vinylidene fluoride series. A value obtained by multiplying the value obtained by dividing the thickness of the polymer powder layer by 100 (100 ⁇ depth of penetration / thickness of vinylidene fluoride polymer powder layer) is defined as N-methyl-2-pyrrolidone permeability.
  • the vinylidene fluoride polymer powder preferably has 80 mol% or more of monomer units derived from vinylidene fluoride.
  • the vinylidene fluoride polymer powder preferably has a polystyrene equivalent weight average molecular weight of 200,000 or more by gel permeation chromatography.
  • the vinylidene fluoride polymer powder has a DSC curve obtained by differential scanning calorimetry having two or more crystal melting peaks, at a lower temperature side than the crystal melting peak (main peak) having the largest peak area, and 110 It is preferable that at least one sub-peak is observed at or above the ° C.
  • the vinylidene fluoride polymer powder preferably has a median diameter of 1 to 250 ⁇ m.
  • the vinylidene fluoride polymer solution of the present invention is obtained from the vinylidene fluoride polymer powder and an aprotic polar solvent.
  • the vinylidene fluoride polymer solution of the present invention is preferably obtained from the vinylidene fluoride polymer powder and N-methyl-2-pyrrolidone.
  • the electrode slurry for an electricity storage device of the present invention is formed from the vinylidene fluoride polymer solution and an active material.
  • the electrode slurry for an electricity storage device of the present invention may be formed from a mixture of the vinylidene fluoride polymer powder and the active material, and an aprotic polar solvent.
  • the electrode for an electricity storage device of the present invention is formed from the electrode slurry for an electricity storage device and a current collector.
  • the vinylidene fluoride polymer powder of the present invention is superior in solubility in aprotic polar solvents such as NMP as compared with conventional vinylidene fluoride polymer powders.
  • FIG. 1 Schematic diagram showing a layer structure inside a glass tube used when performing an N-methyl-2-pyrrolidone permeability test.
  • FIG. 1 Schematic diagram showing a layer structure inside a glass tube used when performing an N-methyl-2-pyrrolidone permeability test.
  • FIG. 1 Schematic diagram showing a layer structure inside a glass tube used when performing an N-methyl-2-pyrrolidone permeability test.
  • FIG. 1 Schematic diagram showing a layer structure inside a glass tube used when performing an N-methyl-2-pyrrolidone permeability test.
  • B In the N-methyl-2-pyrrolidone permeability test, it is a schematic view showing a state after 3 minutes from the injection of N-methyl-2-pyrrolidone stained with methylene blue.
  • the vinylidene fluoride polymer powder of the present invention has an N-methyl-2-pyrrolidone permeability of 12 to 100% in the following N-methyl-2-pyrrolidone permeability test.
  • the vinylidene fluoride polymer powder of the present invention is excellent in the N-methyl-2-pyrrolidone permeability.
  • the N-methyl-2-pyrrolidone permeability is preferably 19 to 100%.
  • vinylidene fluoride polymer powder of the present invention In order to distinguish the vinylidene fluoride polymer powder of the present invention from other vinylidene fluoride polymer powders, they may be referred to as vinylidene fluoride polymer powders (A).
  • N-methyl-2-pyrrolidone permeability test A glass tube with an inner diameter of 8 mm, which is filled with absorbent cotton at the bottom, is erected vertically, and sea sand with a particle size of 0.1 to 0.3 mm is placed on the absorbent cotton.
  • a lower sea sand layer is formed by filling 1 g of the sea sand so that the surface of the sea sand becomes flat, and 1 g of vinylidene fluoride polymer powder is placed on the surface of the lower sea sand layer and the boundary surface with the lower sea sand layer and the fluoride.
  • a vinylidene fluoride polymer powder layer is formed, and the particle size is increased on the surface of the vinylidene fluoride polymer powder layer.
  • An upper sea sand layer is formed by filling 1 g of 0.1 to 0.3 mm of sea sand so that the boundary surface with the vinylidene fluoride polymer powder layer and the surface of the sea sand become flat.
  • N-methyl-2-pyrrolidone dyed with methylene blue (methylene blue concentration: 0.05 mass%) (liquid temperature 23 ° C.) was injected onto the surface of the upper sea sand layer, and 3 minutes after the injection, The penetration depth of N-methyl-2-pyrrolidone dyed with methylene blue into the vinylidene fluoride polymer powder layer and the thickness of the vinylidene fluoride polymer powder layer were measured, and the penetration depth was determined based on the vinylidene fluoride series. A value obtained by multiplying the value obtained by dividing the thickness of the polymer powder layer by 100 (100 ⁇ depth of penetration / thickness of vinylidene fluoride polymer powder layer) is defined as N-methyl-2-pyrrolidone permeability.
  • the N-methyl-2-pyrrolidone permeability test will be further described with reference to FIG.
  • a glass tube having an inner diameter of 8 mm in which absorbent cotton 1 is packed at the bottom is erected in the vertical direction.
  • 1 g of sea sand having a particle size of 0.1 to 0.3 mm is filled on the absorbent cotton 1 so that the surface of the sea sand becomes flat, thereby forming the lower sea sand layer 3.
  • 1 g of vinylidene fluoride polymer powder is filled on the surface of the lower sea sand layer 3 so that the interface with the lower sea sand layer 3 and the surface of the layer formed from the vinylidene fluoride polymer powder are flat.
  • the vinylidene fluoride polymer powder layer 5 is formed.
  • 1 g of sea sand having a particle size of 0.1 to 0.3 mm is placed on the surface of the vinylidene fluoride polymer powder layer 5, and the boundary surface with the vinylidene fluoride polymer powder layer 5 and the surface of the sea sand are flat.
  • the upper sea sand layer 7 is formed by filling to become.
  • a glass tube is usually tapped to flatten the surface.
  • the tap is sufficiently performed (at least 100 times) until the thickness of the layer formed from the vinylidene fluoride polymer powder becomes constant.
  • 5 mL of N-methyl-2-pyrrolidone 9 (methylene blue concentration: 0.05 mass%) (liquid temperature 23 ° C.) stained with methylene blue is injected onto the surface of the upper sea sand layer.
  • the penetration depth D into the vinylidene fluoride polymer powder layer and the thickness L of the vinylidene fluoride polymer powder layer it is necessary to measure the depth and thickness after 3 minutes. . This is because the penetration depth D into the vinylidene fluoride polymer powder layer changes over time, and the thickness L of the vinylidene fluoride polymer powder layer may change over time due to expansion. is there.
  • the vinylidene fluoride polymer powder (A) of the present invention preferably has 80 mol% or more of monomer units derived from vinylidene fluoride, more preferably 90 mol% or more, and more preferably 95 mol% or more. It is most preferable (however, the total monomer unit is 100 mol%). Further, the vinylidene fluoride polymer powder (A) of the present invention preferably has 20 mol% or less of monomer units derived from other monomers other than vinylidene fluoride, and more preferably has 10 mol% or less. It is most preferable to have 5 mol% or less (provided that all monomer units are 100 mol%).
  • the monomer unit derived from vinylidene fluoride When the monomer unit derived from vinylidene fluoride is less than 80 mol%, it tends to easily form mako when the vinylidene fluoride polymer powder (A) of the present invention is dissolved in an aprotic polar solvent. is there.
  • the amount of the monomer unit derived from vinylidene fluoride and the monomer unit derived from another monomer can be determined by a known method such as NMR, elemental analysis, or oxygen flask combustion method.
  • the vinylidene fluoride polymer powder (A) of the present invention preferably has a polystyrene-equivalent weight average molecular weight by gel permeation chromatography (GPC) of 200,000 or more, more preferably 300,000 or more. The most preferable is 500,000 or more.
  • the upper limit of the weight average molecular weight in terms of polystyrene is not particularly limited, but is preferably 4 million or less from the viewpoint of the solubility of the vinylidene fluoride polymer powder in an aprotic polar solvent such as NMP.
  • the vinylidene fluoride polymer powder (A) of the present invention has a DSC curve obtained by differential scanning calorimetry having two or more crystal melting peaks, and from the crystal melting peak (main peak) having the largest peak area. It is preferable that at least one sub-peak is observed on the lower temperature side and 110 ° C. or higher. It is more preferable that at least one sub peak is observed at a lower temperature side than the main peak and at 130 ° C. or higher, and it is particularly preferable that a sub peak is observed at a lower temperature side than the main peak and at 132 to 162 ° C.
  • the crystal melting temperature (Tm) of the vinylidene fluoride polymer powder (A) of the present invention can be determined from the crystal melting peak (main peak) having the largest peak area, and the crystal melting temperature is usually Is 130 to 180 ° C, preferably 140 to 178 ° C.
  • a peak having a smaller peak area than the main peak is referred to as a sub peak, and the sub peak observed at a lower temperature than the main peak is also referred to as a low temperature melting point.
  • the vinylidene fluoride polymer powder (A) of the present invention preferably has a median diameter of 1 to 250 ⁇ m, more preferably 50 to 230 ⁇ m. Within the above range, the vinylidene fluoride polymer powder (A) of the present invention is excellent in solubility and handling properties, which is preferable.
  • the median diameter is the particle diameter corresponding to 50% of the cumulative curve in the particle size distribution, and is also called 50% average particle diameter (dp50).
  • the median diameter is derived on the basis of a volume-based particle size distribution. In this case, the total volume of particles having a larger particle diameter than the value of the median diameter is equal to the total volume of particles having a smaller particle diameter. Become.
  • the vinylidene fluoride polymer powder (A) of the present invention is superior in solubility in an aprotic polar solvent such as NMP as compared with the conventional vinylidene fluoride polymer powder.
  • solubility index is not one, but for example, when vinylidene fluoride polymer powder is dispersed in NMP when the vinylidene fluoride polymer powder is introduced into NMP at room temperature, the It can be judged that the vinylidene chloride polymer powder is superior in solubility as compared with the case where mako is formed.
  • the time until the vinylidene fluoride polymer powder is dissolved when the vinylidene fluoride polymer powder is put into NMP heated to a specific temperature (for example, 50 ° C.) and stirred is short. It can be determined that the solubility is excellent.
  • the obtained vinylidene fluoride polymer solution is preferably a transparent solution. It may be a clear solution. In addition, even when it becomes a translucent liquid, the vinylidene fluoride polymer powder (A) of the present invention can be used without any problem in order to form an electricity storage device electrode slurry and an electricity storage device electrode.
  • the method for producing the vinylidene fluoride polymer powder (A) of the present invention is not particularly limited.
  • the unheat-treated vinylidene fluoride polymer powder has a crystal melting temperature of 100 ° C. or higher.
  • the heat-treated vinylidene fluoride polymer powder corresponds to the vinylidene fluoride polymer powder (A) of the present invention.
  • the unheat-treated vinylidene fluoride polymer powder is more suitable for an aprotic polar solvent such as NMP than the vinylidene fluoride polymer powder (A) of the present invention (heat-treated vinylidene fluoride polymer powder). Poor solubility.
  • the first aspect of the heat treatment is characterized by subjecting the unheat-treated vinylidene fluoride polymer powder to a heat treatment at a temperature at which the polymer powder is 125 ° C. or higher and lower than the crystal melting temperature (Tm).
  • Tm crystal melting temperature
  • heat treatment is performed on the unheat-treated vinylidene fluoride polymer powder at a temperature at which the polymer powder is 100 ° C. or higher and lower than the crystal melting temperature (Tm) under high shear.
  • Tm crystal melting temperature
  • heat treatment is performed while stirring the polymer powder using a Henschel mixer or the like, and the heat treatment is performed under high shear with a peripheral speed of stirring of 1 m / s or more, preferably 3 to 100 m / s. It is characterized by that.
  • the heat-treated vinylidene fluoride polymer powder obtained by the production method corresponds to the vinylidene fluoride polymer powder (A) of the present invention, and compared with the conventional vinylidene fluoride polymer powder, non-MPN or the like. Excellent solubility in protic polar solvents.
  • the said heat processing is a process which hold
  • the heat treatment in the present invention is such a vinylidene fluoride polymer. It is not a treatment in which the temperature of the powder itself is not sufficiently increased, but a treatment in which the temperature of the vinylidene fluoride polymer powder itself is 100 ° C. or higher and lower than the crystal melting temperature (Tm) of the unheat-treated vinylidene fluoride polymer powder. means.
  • the unheated vinylidene fluoride polymer powder will be described below.
  • the unheated vinylidene fluoride polymer powder means a vinylidene fluoride polymer powder that has not been heat-treated as described below, and conventionally known vinylidene fluoride polymer powder can be used.
  • the unheat-treated vinylidene fluoride polymer powder may be a polymer powder having a monomer unit derived from vinylidene fluoride.
  • the polymer having a monomer unit derived from vinylidene fluoride is not particularly limited, but a homopolymer of vinylidene fluoride, a copolymer of vinylidene fluoride and other monomers, or a modification of a homopolymer of vinylidene fluoride And modified products of copolymers of vinylidene fluoride and other monomers. These polymers are usually used alone or in combination of two or more.
  • Examples of the other monomer include a carboxyl group-containing monomer, a carboxylic acid anhydride group-containing monomer, a fluorine-containing monomer excluding vinylidene fluoride, and an ⁇ -olefin.
  • a carboxyl group-containing monomer a carboxylic acid anhydride group-containing monomer
  • a fluorine-containing monomer excluding vinylidene fluoride a fluorine-containing monomer excluding vinylidene fluoride
  • an ⁇ -olefin a monomer that may be used by 2 or more types.
  • carboxyl group-containing monomer unsaturated monobasic acids, unsaturated dibasic acids, monoesters of unsaturated dibasic acids, and the like are preferable, and monoesters of unsaturated dibasic acids and unsaturated dibasic acids are more preferable.
  • Examples of the unsaturated monobasic acid include acrylic acid.
  • Examples of the unsaturated dibasic acid include maleic acid and citraconic acid.
  • the unsaturated dibasic acid monoester preferably has 5 to 8 carbon atoms, and examples thereof include maleic acid monomethyl ester, maleic acid monoethyl ester, citraconic acid monomethyl ester, and citraconic acid monoethyl ester. Can do.
  • maleic acid citraconic acid
  • maleic acid monomethyl ester maleic acid monomethyl ester
  • citraconic acid monomethyl ester maleic acid monomethyl ester
  • Examples of the carboxylic acid anhydride group-containing monomer include unsaturated dibasic acid anhydrides, and examples of the unsaturated dibasic acid anhydride include maleic anhydride and citraconic anhydride.
  • fluorine-containing monomer excluding vinylidene fluoride examples include vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, and hexafluoropropylene.
  • ⁇ -Olefin includes ethylene, propylene, 1-butene and the like.
  • the copolymer of vinylidene fluoride and other monomers is preferably a copolymer of vinylidene fluoride and maleic acid monomethyl ester, a copolymer of vinylidene fluoride, hexafluoropropylene and maleic acid monomethyl ester, or the like. It is done.
  • a copolymer of vinylidene fluoride and another monomer can be obtained by copolymerizing vinylidene fluoride and the other monomer.
  • the method of homopolymerizing vinylidene fluoride and the method of copolymerizing vinylidene fluoride and other monomers are not particularly limited, and can be obtained by a polymerization method such as suspension polymerization, emulsion polymerization, or solution polymerization.
  • polymerization conditions such as polymerization temperature can be arbitrarily set.
  • the polymerization temperature is usually in the range of 20 to 120 ° C, preferably in the range of 25 to 100 ° C, and most preferably in the range of 25 to 75 ° C.
  • the vinylidene fluoride polymer powder obtained by suspension polymerization at a polymerization temperature in the range of 25 to 75 ° C. is used as the unheated vinylidene fluoride polymer powder
  • the resulting heat-treated vinylidene fluoride polymer powder The polymer powder is preferred because it tends to be excellent in solubility in an aprotic polar solvent such as NMP.
  • the polymerization method is preferably suspension polymerization or emulsion polymerization, and more preferably suspension polymerization, in which a polymer having monomer units derived from vinylidene fluoride in a powder state can be obtained.
  • the unheat-treated vinylidene fluoride polymer powder may be the polymer itself when the polymer having a vinylidene fluoride-derived monomer unit is obtained by a polymerization method obtained in a powder state. It may be a polymer having a specific particle diameter obtained by sorting with a sieve or the like.
  • the unheat-treated vinylidene fluoride polymer powder is obtained by a polymerization method in which a polymer having a monomer unit derived from vinylidene fluoride is obtained in a bulk state
  • the polymer is, for example, It may be a polymer formed into a powder by freeze pulverization using liquid nitrogen described in JP-A-6-108103.
  • a modified product of a homopolymer of vinylidene fluoride or a copolymer of a copolymer of vinylidene fluoride and another monomer includes the homopolymer of vinylidene fluoride or a copolymer of vinylidene fluoride and another monomer.
  • the polymer can be obtained by modification.
  • the unheat-treated vinylidene fluoride polymer powder preferably has 80 mol% or more of monomer units derived from vinylidene fluoride, more preferably 90 mol% or more, most preferably 95 mol% or more (provided that 100% by mole of all monomer units).
  • the unheat-treated vinylidene fluoride polymer powder preferably has a monomer unit derived from another monomer other than vinylidene fluoride, preferably 20 mol% or less, more preferably 10 mol% or less, and more preferably 5 mol. % Is most preferable (provided that the total monomer units are 100 mol%).
  • the melting point of the unheat-treated vinylidene fluoride polymer powder may be lowered and may be easily fused during heat treatment. Becomes difficult.
  • the ratio of the monomer unit derived from vinylidene fluoride of the vinylidene fluoride polymer powder does not change, the ratio of the monomer unit derived from vinylidene fluoride of the unheat treated vinylidene fluoride polymer powder,
  • the proportion of the monomer unit derived from vinylidene fluoride in the vinylidene fluoride polymer powder (A) (heat-treated vinylidene fluoride polymer powder) of the present invention is the same.
  • the amount of monomer units derived from vinylidene fluoride and monomer units derived from other monomers can be determined by known methods such as NMR, elemental analysis, oxygen flask combustion method and the like.
  • the unheat-treated vinylidene fluoride polymer powder preferably has a polystyrene equivalent weight average molecular weight of 200,000 or more by gel permeation chromatography (GPC), more preferably 300,000 or more, and 50 Most preferably, it is 10,000 or more.
  • the upper limit of the weight average molecular weight in terms of polystyrene is not particularly limited, but is 4 million or less from the viewpoint of the solubility of the vinylidene fluoride polymer powder of the present invention in an aprotic polar solvent such as NMP. Is preferred.
  • the weight average molecular weight of the vinylidene fluoride polymer powder does not change in the heat treatment described later, the weight average molecular weight of the unheat treated vinylidene fluoride polymer powder and the vinylidene fluoride polymer powder (A ) (Heat-treated vinylidene fluoride polymer powder) agrees with the weight average molecular weight.
  • the median diameter of the unheat-treated vinylidene fluoride polymer powder is preferably 1 to 250 ⁇ m, and more preferably 50 to 230 ⁇ m. Within the above range, the heat-treated vinylidene fluoride polymer powder is excellent in solubility and handling properties, which is preferable. In addition, the median diameter of the vinylidene fluoride polymer powder may be changed by a heat treatment described later.
  • the inherent viscosity of the non-heat treated vinylidene fluoride polymer powder is preferably 0.3 to 10 dl / g, more preferably 1 to 5 dl / g. Within the said range, the mechanical property of the heat-treated vinylidene fluoride polymer obtained is good, and the handleability of the solution is also good.
  • the crystal melting temperature (Tm) of the unheat-treated vinylidene fluoride polymer powder is usually 130 to 180 ° C.
  • the crystal melting temperature can be determined from a DSC curve obtained by differential scanning calorimetry (hereinafter also referred to as DSC). In the DSC curve, when there are a plurality of crystal melting peaks (endothermic peaks), the crystal melting temperature (Tm) is determined based on the peak having the maximum peak area.
  • a commercially available product may be used as the unheated vinylidene fluoride polymer powder.
  • the unheat-treated vinylidene fluoride polymer powder is subjected to a heat treatment at a temperature at which the polymer powder is 100 ° C. or higher and lower than the crystal melting temperature (Tm).
  • the heat treatment is a treatment for holding the polymer powder at a temperature at which the temperature of the unheated vinylidene fluoride polymer powder itself is 100 ° C. or higher and lower than the crystal melting temperature (Tm). That is, in the temporary heating such as air drying, the temperature of the vinylidene fluoride polymer powder itself is lower than the hot air temperature.
  • the heat treatment in the present invention is such a vinylidene fluoride polymer. It is not a treatment in which the temperature of the powder itself is not sufficiently increased, but a treatment in which the temperature of the vinylidene fluoride polymer powder itself is 100 ° C. or higher and lower than the crystal melting temperature (Tm) of the unheat-treated vinylidene fluoride polymer powder. means.
  • the heat processing temperature is 180 degrees C or less, and it is more preferable that it is 160 degrees C or less.
  • the heat processing temperature is 180 degrees C or less, and it is more preferable that it is 160 degrees C or less.
  • the first aspect of the heat treatment is characterized by subjecting the unheat-treated vinylidene fluoride polymer powder to a heat treatment at a temperature at which the polymer powder is 125 ° C. or higher and lower than the crystal melting temperature (Tm).
  • Tm crystal melting temperature
  • heat treatment is performed on the unheat-treated vinylidene fluoride polymer powder at a temperature at which the polymer powder is 100 ° C. or higher and lower than the crystal melting temperature (Tm) under high shear.
  • Tm crystal melting temperature
  • heat treatment is performed while stirring the polymer powder using a Henschel mixer or the like, and the heat treatment is performed under high shear with a peripheral speed of stirring of 1 m / s or more, preferably 3 to 100 m / s. It is characterized by.
  • heat treatment is performed on unheat-treated vinylidene fluoride polymer powder at a temperature at which the polymer powder is 130 ° C. or higher, preferably 135 ° C. or higher and lower than the crystal melting temperature (Tm).
  • Tm crystal melting temperature
  • the unheat-treated vinylidene fluoride polymer powder has a polymer powder of 110 ° C. or higher, preferably 125 ° C. or higher and less than the crystal melting temperature (Tm).
  • Tm crystal melting temperature
  • lifted the lower limit of the heat treatment temperature in the preferred embodiment of the second embodiment is 110 ° C. or higher, preferably 125 ° C. or higher.
  • the heat treatment temperature is lower in the second embodiment in which the heat treatment is performed under high shear than in the first embodiment in which the unheated vinylidene fluoride polymer powder is allowed to stand.
  • the vinylidene fluoride polymer powder (A) of the present invention can be obtained. The reason for this is not clear, but the present inventors generate strong friction on the surface of the polymer powder under high shear, and the structure near the surface of the polymer powder changes due to the effect of frictional heat. It was estimated that the vinylidene fluoride polymer powder of the present invention can be obtained even when heat treatment is performed at a temperature lower than that of the embodiment.
  • the heat treatment time in the heat treatment is not particularly limited, but is usually 10 seconds to 20 hours, more preferably 60 seconds to 20 hours, and most preferably 60 seconds to 5 hours.
  • the heat processing time in this invention means the time when the temperature of polymer powder itself is in the range of the said heat processing temperature.
  • the atmosphere when the heat treatment is performed there is no particular limitation on the atmosphere when the heat treatment is performed, and for example, it can be performed in an air atmosphere or a nitrogen atmosphere.
  • the heat treatment can be carried out under reduced pressure, under increased pressure or under normal pressure, but is usually carried out under normal pressure.
  • the method of performing the heat treatment is not particularly limited, and examples thereof include a method using a hot air circulating furnace, a method using a Henschel mixer, and a method using a gear oven.
  • the heat treatment when performed in a hot air circulating furnace, for example, it can be performed by installing a box containing unheat-treated vinylidene fluoride polymer powder in the hot air circulating furnace.
  • it when performing heat processing with a Henschel mixer, it can carry out, for example by putting unheat-treated vinylidene fluoride polymer powder in a Henschel mixer and heating it with stirring.
  • the vinylidene fluoride polymer solution of the present invention is obtained from the vinylidene fluoride polymer powder (A) (heat treated vinylidene fluoride polymer powder) and an aprotic polar solvent.
  • the vinylidene fluoride polymer powder (A) can be dissolved in an aprotic polar solvent such as NMP more rapidly than the conventional vinylidene fluoride polymer powder.
  • Examples of the aprotic polar solvent include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide and the like, and among them, N-methyl-2-pyrrolidone is preferable.
  • the amount of the aprotic polar solvent constituting the vinylidene fluoride polymer solution is not particularly limited, but is usually 400 to 10,000 weights with respect to 100 parts by weight of the vinylidene fluoride polymer powder (A). Parts, preferably 550 to 2400 parts by weight.
  • the vinylidene fluoride polymer powder (A) is usually added to an aprotic polar solvent and stirred.
  • the vinylidene fluoride polymer powder (A) is preferably dissolved in an aprotic polar solvent having a liquid temperature of 35 to 130 ° C. More preferably, the vinylidene chloride polymer powder (A) is dissolved in N-methyl-2-pyrrolidone having a liquid temperature of 35 to 130 ° C.
  • N-methyl-2-pyrrolidone is used as the aprotic polar solvent, the liquid temperature is 45 to 80 ° C., from the viewpoint of the solubility of the vinylidene fluoride polymer powder (A). Is particularly preferred.
  • the aprotic polar solvent heated to 35 to 130 ° C As a method for dissolving the vinylidene fluoride polymer powder (A) in an aprotic polar solvent having a liquid temperature of 35 to 130 ° C., the aprotic polar solvent heated to 35 to 130 ° C.
  • the above-mentioned vinylidene fluoride polymer powder (A) is charged into an aprotic polar solvent at room temperature and stirred at high speed using a homogenizer, a disper mixer, etc. Examples thereof include a method of dissolving by heating to 130 ° C.
  • the vinylidene fluoride polymer powder (A) is dissolved in an aprotic polar solvent, a stirrer using a homogenizer, a disper mixer, a propeller blade, etc. K. Fill mix, ultrasonic vibration, or the like can be used. Moreover, the apparatus provided with the heating jacket etc. may be sufficient as needed.
  • the electrode slurry for an electricity storage device of the present invention is formed from the vinylidene fluoride polymer solution and an active material (first aspect), or a mixture of the vinylidene fluoride polymer powder (A) and an active material And an aprotic polar solvent (second embodiment).
  • a nonaqueous electrolyte secondary battery for example, lithium ion secondary battery
  • an electric double layer capacitor etc.
  • the electrode slurry for an electricity storage device of the present invention is particularly preferably used when forming a positive electrode of a nonaqueous electrolyte secondary battery.
  • the electrode slurry for the electricity storage device of the first aspect can be obtained by mixing the vinylidene fluoride polymer solution with an active material.
  • a planetary mixer, a kneader, an internal mixer, Primix Co., Ltd. T. K. A fill mix or the like can be used.
  • the electrode slurry for an electricity storage device is obtained by first mixing the vinylidene fluoride polymer powder (A) and an active material to obtain a mixture.
  • a planetary mixer, a paddle mixer, A Henschel mixer, a ribbon mixer, or the like can be used.
  • the obtained mixture is obtained by mixing with an aprotic polar solvent.
  • a planetary mixer, a kneader, an internal mixer, T.M. K. A fill mix or the like can be used.
  • the aprotic polar solvent used in the second embodiment the aprotic polar solvent described in the section ⁇ vinylidene fluoride polymer solution> can be used.
  • the amount of the aprotic polar solvent used in the second embodiment is not particularly limited, but is usually 400 to 10,000 parts by weight, preferably 100 parts by weight with respect to 100 parts by weight of the vinylidene fluoride polymer powder (A). Is used in the range of 550 to 2400 parts by weight.
  • the amount of the active material contained in the electrode slurry for the electricity storage device is not particularly limited, but usually the vinylidene fluoride polymer powder (A) (first) contained in the vinylidene fluoride polymer solution.
  • One aspect) 100 parts by weight or 100 parts by weight of vinylidene fluoride polymer powder (A) (second aspect) is usually 100 to 10,000 parts by weight, preferably 900 to 6400 parts by weight. is there.
  • examples of the active material include carbon materials, metal / alloy materials, metal oxides, etc. Among them, metal oxides are preferable.
  • the electrode for an electricity storage device of the present invention is formed from the electrode slurry for an electricity storage device and a current collector.
  • it is formed by applying and drying the electrode slurry for an electricity storage device on a current collector.
  • Examples of the current collector include copper, aluminum, nickel, and gold, and examples of the shape include a metal foil and a metal net.
  • the electrode slurry for the electricity storage device when applying the electrode slurry for the electricity storage device to the current collector, it is applied to at least one surface, preferably both surfaces of the current collector.
  • the method for coating is not particularly limited, and examples thereof include a method using a bar coater, a die coater, or a comma coater.
  • drying performed after the coating is usually performed at a temperature of 50 to 150 ° C. for 1 to 300 minutes.
  • the pressure at the time of drying is not particularly limited, but it is usually carried out under atmospheric pressure or reduced pressure.
  • Samples (the following vinylidene fluoride polymer powders (1) to (9) and heat-treated vinylidene fluoride polymer powders obtained in the following examples and comparative examples (provided that Comparative Example 1, In 3 to 10, about 2.0 mg of vinylidene fluoride polymer powder)) was precisely weighed. While flowing nitrogen at a flow rate of 50 mL / min, the temperature was raised from 30 ° C. to 230 ° C. at a rate of 5 ° C./min. During this time, temperature modulation of ⁇ 0.53 ° C./40 sec was applied.
  • ⁇ rel sample solution drop seconds / solvent drop seconds
  • C sample solution concentration (0.4 g / dl).
  • the point when the solid matter or gel-like material derived from the vinylidene fluoride polymer powder disappears is not only when the solution becomes a transparent state, but also when the solution is a semi-transparent state without any solid matter or gel-like matter. In this case, the dissolution was completed.
  • the time from the setting to the water bath until the dissolution was completed was defined as the dissolution time.
  • N-methyl-2-pyrrolidone permeability was determined by the following N-methyl-2-pyrrolidone permeability test.
  • the bottom of a glass tube having a length of 25 cm and an inner diameter of 8 mm was filled with round absorbent cotton, and the glass tube was held vertically.
  • 1 g of sea sand (manufactured by Kanto Chemical Co., Ltd., particle size: 0.1 to 0.3 mm) was poured onto the absorbent cotton and tapped several times to make the surface of the sea sand flat to form a lower sea sand layer.
  • the heat-treated vinylidene fluoride polymer powder obtained in the following Examples and Comparative Examples so that the boundary surface with the sea sand layer is flat on the lower sea sand layer (however, in Comparative Examples 1, 3 to 10)
  • a vinylidene fluoride polymer powder layer was formed on the lower sea sand.
  • sea sand manufactured by Kanto Chemical Co., Ltd., particle size: 0.1 to 0.3 mm
  • the surface of the sea sand was flattened by tapping lightly several times so that the interface between the sea sand and PVDF did not collapse.
  • N-methyl-2-pyrrolidone stained with methylene blue (methylene blue concentration: 0.05% by mass) (liquid temperature: 23 ° C.) from the upper part of the glass tube onto the surface of the upper sea sand layer using a 5 mL volume pipette. ) 5 mL was injected.
  • the penetration depth of N-methyl-2-pyrrolidone stained with methylene blue and the thickness of the vinylidene fluoride polymer powder layer after 3 minutes from the injection of N-methyl-2-pyrrolidone stained with methylene blue It was measured. When the penetration depth is not constant, the average value of the portion with the deepest penetration depth and the portion with the shallowest penetration depth is defined as the penetration depth.
  • the thickness of the vinylidene fluoride polymer powder layer refers to the boundary between the lower sea sand layer and the vinylidene fluoride polymer powder layer to the interface between the upper sea sand layer and the vinylidene fluoride polymer powder layer. Distance.
  • the value obtained by dividing the penetration depth by the thickness of the vinylidene fluoride polymer powder layer multiplied by 100 (100 ⁇ depth of penetration / vinylidene fluoride polymer powder layer thickness) is N-methyl. Obtained as -2-pyrrolidone penetration rate.
  • N-methyl-2-pyrrolidone permeability is also simply referred to as the permeability.
  • [Production Example 1] (Production of vinylidene fluoride polymer powder (1)) Charge each volume of 1040 g of ion-exchanged water, 0.4 g of methylcellulose, 400 g of vinylidene fluoride monomer, 0.6 g of perbutyl peroxypivalate, and 1.2 g of diethyl carbonate in a 2 liter autoclave and suspend at 65 ° C. for 7 hours. Polymerization was performed.
  • the obtained polymer slurry was heat treated at 95 ° C. for 30 minutes, dehydrated, washed with water, and further dried at 80 ° C. for 20 hours to obtain a vinylidene fluoride polymer powder (1).
  • the obtained vinylidene fluoride polymer powder (1) had an inherent viscosity of 2.3 dl / g, a weight average molecular weight of 850,000, a median diameter of 194 ⁇ m, and a Tm of 169 ° C.
  • the obtained polymer slurry was heat treated at 95 ° C. for 30 minutes, dehydrated, washed with water, and further dried at 80 ° C. for 20 hours to obtain a vinylidene fluoride polymer powder (2).
  • the inherent viscosity of the obtained vinylidene fluoride polymer powder (2) was 2.2 dl / g, the weight average molecular weight was 770,000, the median diameter was 195 ⁇ m, and Tm was 171 ° C.
  • the vinylidene fluoride polymer powder (2) was analyzed for chlorine content according to JIS K7229, and 1.1 mol% was introduced in terms of chlorotrifluoroethylene monomer, that is, vinylidene fluoride polymer powder ( It was confirmed that 2) had 98.9 mol% of monomer units derived from vinylidene fluoride.
  • the obtained polymer slurry was heat treated at 95 ° C. for 30 minutes, dehydrated, washed with water, and further dried to obtain a vinylidene fluoride polymer powder (3). Drying was performed using a flash dryer under conditions of a hot air inlet temperature of 140 ° C. and a hot air outlet temperature of 80 ° C.
  • the resulting vinylidene fluoride polymer powder (3) had an inherent viscosity of 1.1 dl / g, a weight average molecular weight of 300,000, a median diameter of 210 ⁇ m, and a Tm of 173 ° C.
  • the resulting polymer slurry was heat treated at 95 ° C. for 30 minutes, dehydrated, washed with water, and further dried to obtain a vinylidene fluoride polymer powder (4). Drying was performed using a flash dryer under conditions of a hot air inlet temperature of 140 ° C. and a hot air outlet temperature of 80 ° C.
  • the obtained vinylidene fluoride polymer powder (4) had an inherent viscosity of 1.3 dl / g, a weight average molecular weight of 350,000, a median diameter of 184 ⁇ m, and a Tm of 173 ° C.
  • the obtained polymer slurry was heat treated at 95 ° C. for 30 minutes, dehydrated, washed with water, and further dried to obtain a vinylidene fluoride polymer powder (5). Drying was performed using a flash dryer under conditions of a hot air inlet temperature of 140 ° C. and a hot air outlet temperature of 80 ° C.
  • the resulting vinylidene fluoride polymer powder (5) had an inherent viscosity of 2.2 dl / g, a weight average molecular weight of 770,000, a median diameter of 215 ⁇ m, and a Tm of 173 ° C.
  • the obtained polymer slurry was heat treated at 95 ° C. for 30 minutes, dehydrated, washed with water, and further dried to obtain a vinylidene fluoride polymer powder (6). Drying was performed using a flash dryer under conditions of a hot air inlet temperature of 140 ° C. and a hot air outlet temperature of 80 ° C.
  • the obtained vinylidene fluoride polymer powder (6) had an inherent viscosity of 3.1 dl / g, a weight average molecular weight of 1.1 million, a median diameter of 220 ⁇ m, and a Tm of 173 ° C.
  • the obtained polymer slurry was heat treated at 95 ° C. for 30 minutes, dehydrated, washed with water, and further dried to obtain a vinylidene fluoride polymer powder (7). Drying was performed using a flash dryer under conditions of a hot air inlet temperature of 140 ° C. and a hot air outlet temperature of 80 ° C.
  • the inherent viscosity of the obtained vinylidene fluoride polymer powder (7) was 2.2 dl / g, the weight average molecular weight was 770,000, the median diameter was 203 ⁇ m, and Tm was 171 ° C.
  • Vinylidene fluoride polymer powder (8) Vinylidene fluoride polymer powder (8)
  • PVDF powder manufactured by Solvay Solexis Co., Ltd. trade name solf6020 was used as the vinylidene fluoride polymer powder (8).
  • Solef 6020 had an inherent viscosity of 1.85 dl / g, a weight average molecular weight of 600,000, a median diameter of 104 ⁇ m, and a Tm of 170 ° C.
  • PVDF powder manufactured by Arkema, trade name kynar HSV900 was used.
  • kynar HSV900 had an inherent viscosity of 1.0 dl / g, a weight average molecular weight of 660,000, a median diameter of 5 ⁇ m, and a Tm of 160 ° C.
  • the above-mentioned vinylidene fluoride polymer powders (1) to (9) correspond to the unheated vinylidene fluoride polymer powder because they are not heat-treated.
  • Example 1 In a kraft paper box having a width of 10 cm, a length of 15 cm, and a height of 3 cm, 10 g of vinylidene fluoride polymer powder (6) is placed, and the vinylidene fluoride polymer powder (6) has a uniform thickness. I spread it in the box.
  • the kraft paper box is covered with kraft paper, and the capped box is placed in a hot air circulating furnace (manufactured by Yamato Kagaku, trade name FineOven DH410) at a temperature of 130 ° C., and vinylidene fluoride polymer
  • the temperature of the powder (6) itself was increased to 110 ° C. over 30 seconds from the time when the temperature reached 100 ° C., further increased to 120 ° C. over 54 seconds, and further increased to 125 ° C. over 54 seconds. Further, the temperature was raised to 130 ° C. over 5 minutes and held at 130 ° C. for 52 minutes, and then the covered box was taken out from the hot air circulation furnace and allowed to cool at room temperature, whereby a heat-treated vinylidene fluoride polymer was obtained.
  • a powder (1) was obtained.
  • Example 2 As in Example 1, 10 g of vinylidene fluoride polymer powder (6) is placed in a kraft paper box having a width of 10 cm, a length of 15 cm, and a height of 3 cm, and vinylidene fluoride polymer powder (6 ) was spread in a box so that the thickness was uniform.
  • the box made of kraft paper is covered with kraft paper, and the box with the lid is placed in a hot air circulating furnace (trade name FineOven DH410, manufactured by Yamato Kagaku) at a temperature of 135 ° C., and vinylidene fluoride polymer
  • the temperature of the powder (6) itself was increased to 110 ° C. over 30 seconds from the time when the temperature reached 100 ° C., further increased to 120 ° C. over 42 seconds, and further increased to 125 ° C. over 30 seconds.
  • the temperature was further raised to 130 ° C. over 1 minute, further heated to 135 ° C. over 5 minutes, held at 135 ° C. for 52 minutes, the lidded box was taken out of the hot air circulation furnace and allowed to cool at room temperature.
  • a heat-treated vinylidene fluoride polymer powder (2) was obtained.
  • Example 3 As in Example 1, 10 g of vinylidene fluoride polymer powder (6) is placed in a kraft paper box having a width of 10 cm, a length of 15 cm, and a height of 3 cm, and vinylidene fluoride polymer powder (6 ) was spread in a box so that the thickness was uniform.
  • the box made of kraft paper is covered with kraft paper, and the box with the lid is put in a hot air circulating furnace (product name: FineOven DH410, manufactured by Yamato Kagaku) at a temperature of 140 ° C., and vinylidene fluoride polymer
  • the temperature of the powder (6) itself was raised to 110 ° C. over 24 seconds from the time when the temperature of the powder (6) itself reached 100 ° C., further raised to 120 ° C. over 30 seconds, and further raised to 125 ° C. over 24 seconds.
  • the temperature is further raised to 130 ° C. over 30 seconds, further raised to 135 ° C. over 54 seconds, further raised to 140 ° C. over 5 minutes, held at 140 ° C. for 52 minutes, and then the box covered.
  • Example 4 As in Example 1, 10 g of vinylidene fluoride polymer powder (6) is placed in a kraft paper box having a width of 10 cm, a length of 15 cm, and a height of 3 cm, and vinylidene fluoride polymer powder (6 ) was spread in a box so that the thickness was uniform.
  • the box made of kraft paper is covered with kraft paper, and the box with the lid is put in a hot air circulating furnace (manufactured by Yamato Kagaku, trade name FineOven DH410) at a temperature of 150 ° C., and vinylidene fluoride polymer
  • the temperature of the powder (6) itself was increased to 110 ° C. over 18 seconds from the time when the temperature of the powder (6) itself reached 100 ° C., further increased to 120 ° C. over 24 seconds, and further increased to 125 ° C. over 12 seconds.
  • the temperature is further raised to 130 ° C. over 18 seconds, further raised to 135 ° C. over 24 seconds, further raised to 140 ° C. over 30 seconds, further raised to 150 ° C. over 6 minutes
  • the covered box was taken out of the hot air circulating furnace and allowed to cool at room temperature to obtain a heat-treated vinylidene fluoride polymer powder (4).
  • Example 5 As in Example 1, 10 g of vinylidene fluoride polymer powder (6) is placed in a kraft paper box having a width of 10 cm, a length of 15 cm, and a height of 3 cm, and vinylidene fluoride polymer powder (6 ) was spread in a box so that the thickness was uniform.
  • the box made of kraft paper is covered with kraft paper, and the box with the lid is put into a hot air circulating furnace (manufactured by Yamato Kagaku, trade name FineOven DH410) at a temperature of 160 ° C., and vinylidene fluoride polymer
  • the temperature of the powder (6) itself was raised to 110 ° C. over 12 seconds from the time when the temperature of the powder (6) itself reached 100 ° C., further raised to 120 ° C. over 18 seconds, and further raised to 125 ° C. over 12 seconds.
  • the temperature is further raised to 130 ° C. over 12 seconds, further raised to 135 ° C. over 18 seconds, further raised to 140 ° C. over 18 seconds, further raised to 150 ° C.
  • Example 6 As in Example 1, 10 g of vinylidene fluoride polymer powder (6) is placed in a kraft paper box having a width of 10 cm, a length of 15 cm, and a height of 3 cm, and vinylidene fluoride polymer powder (6 ) was spread in a box so that the thickness was uniform.
  • the box made of kraft paper is covered with kraft paper, and the box with the lid is put in a hot-air circulating furnace (manufactured by Yamato Kagaku, trade name FineOven DH410) at a temperature of 125 ° C., and vinylidene fluoride polymer
  • the temperature of the powder (6) itself was increased to 110 ° C. over 42 seconds from the time when the temperature of the powder (6) itself reached 100 ° C., further increased to 120 ° C. over 84 seconds, and further increased to 125 ° C. over 5 minutes.
  • the covered box was taken out from the hot air circulation furnace and allowed to cool at room temperature to obtain a heat-treated vinylidene fluoride polymer powder (6).
  • Example 7 As in Example 1, 10 g of vinylidene fluoride polymer powder (6) is placed in a kraft paper box having a width of 10 cm, a length of 15 cm, and a height of 3 cm, and vinylidene fluoride polymer powder (6 ) was spread in a box so that the thickness was uniform.
  • the box made of kraft paper is covered with kraft paper, and the box with the lid is put in a hot air circulating furnace (manufactured by Yamato Kagaku, trade name FineOven DH410) at a temperature of 130 ° C., and vinylidene fluoride polymer
  • the temperature of the powder (6) itself was increased to 110 ° C. over 30 seconds from the time when the temperature reached 100 ° C., further increased to 120 ° C. over 54 seconds, and further increased to 125 ° C. over 54 seconds.
  • the temperature is further raised to 130 ° C. over 5 minutes and held at 130 ° C. for 19 hours and 52 minutes, and then the lidded box is taken out from the hot air circulation furnace and allowed to cool at room temperature, whereby the heat-treated vinylidene fluoride system A polymer powder (7) was obtained.
  • vinylidene fluoride polymer powder (6) not subjected to the heat treatment obtained in Production Example 6 is also referred to as a vinylidene fluoride polymer powder (c1).
  • Example 2 As in Example 1, 10 g of vinylidene fluoride polymer powder (6) is placed in a kraft paper box having a width of 10 cm, a length of 15 cm, and a height of 3 cm, and vinylidene fluoride polymer powder (6 ) was spread in a box so that the thickness was uniform.
  • the box made of kraft paper is covered with kraft paper, and the box with the lid is placed in a hot air circulating furnace (manufactured by Yamato Kagaku, trade name FineOven DH410) at a temperature of 120 ° C., and vinylidene fluoride polymer
  • a hot air circulating furnace manufactured by Yamato Kagaku, trade name FineOven DH410
  • vinylidene fluoride polymer After the temperature of the powder (6) itself reached 100 ° C., the temperature was raised to 110 ° C. over 1 minute, further raised to 120 ° C. over 6 minutes, held at 120 ° C. for 54 minutes, The box was removed from the hot air circulating furnace and allowed to cool at room temperature to obtain a heat-treated vinylidene fluoride polymer powder (c2).
  • Example 8 A heat-treated vinylidene fluoride polymer powder (8) was obtained in the same manner as in Example 3 except that the vinylidene fluoride polymer powder (6) was replaced with the vinylidene fluoride polymer powder (2). .
  • the vinylidene fluoride polymer powder (2) not subjected to the heat treatment obtained in Production Example 2 is also referred to as a vinylidene fluoride polymer powder (c3).
  • Example 9 A heat-treated vinylidene fluoride polymer powder (9) was obtained in the same manner as in Example 1 except that the vinylidene fluoride polymer powder (6) was replaced with the vinylidene fluoride polymer powder (3). .
  • Example 10 A heat-treated vinylidene fluoride polymer powder (10) was obtained in the same manner as in Example 3, except that the vinylidene fluoride polymer powder (6) was replaced with the vinylidene fluoride polymer powder (3). .
  • vinylidene fluoride polymer powder (3) not subjected to the heat treatment obtained in Production Example 3 is also referred to as vinylidene fluoride polymer powder (c4).
  • Example 11 A heat-treated vinylidene fluoride polymer powder (11) was obtained in the same manner as in Example 3 except that the vinylidene fluoride polymer powder (6) was replaced with the vinylidene fluoride polymer powder (4). .
  • the vinylidene fluoride polymer powder (4) not subjected to the heat treatment obtained in Production Example 4 is also referred to as a vinylidene fluoride polymer powder (c5).
  • Example 12 A heat-treated vinylidene fluoride polymer powder (12) was obtained in the same manner as in Example 3 except that the vinylidene fluoride polymer powder (6) was replaced with the vinylidene fluoride polymer powder (5). .
  • vinylidene fluoride polymer powder (5) not subjected to the heat treatment obtained in Production Example 5 is also referred to as vinylidene fluoride polymer powder (c6).
  • Example 13 A heat-treated vinylidene fluoride polymer powder (13) was obtained in the same manner as in Example 1 except that the vinylidene fluoride polymer powder (6) was replaced with the vinylidene fluoride polymer powder (8). .
  • Example 14 A heat-treated vinylidene fluoride polymer powder (14) was obtained in the same manner as in Example 3 except that the vinylidene fluoride polymer powder (6) was replaced with the vinylidene fluoride polymer powder (8). .
  • the vinylidene fluoride polymer powder (8) is also referred to as vinylidene fluoride polymer powder (c7).
  • Example 15 A heat-treated vinylidene fluoride polymer powder (15) was obtained in the same manner as in Example 4 except that the vinylidene fluoride polymer powder (6) was replaced with the vinylidene fluoride polymer powder (9). .
  • the vinylidene fluoride polymer powder (9) is also referred to as vinylidene fluoride polymer powder (c8).
  • Example 16 A heat-treated vinylidene fluoride polymer powder (16) was obtained in the same manner as in Example 3 except that the vinylidene fluoride polymer powder (6) was replaced with the vinylidene fluoride polymer powder (7). .
  • vinylidene fluoride polymer powder (7) not subjected to the heat treatment obtained in Production Example 7 is also referred to as vinylidene fluoride polymer powder (c9).
  • Example 17 A heat-treated vinylidene fluoride polymer powder (17) was obtained in the same manner as in Example 4 except that the vinylidene fluoride polymer powder (6) was replaced with the vinylidene fluoride polymer powder (1). .
  • the vinylidene fluoride polymer powder (1) not subjected to the heat treatment obtained in Production Example 1 is also referred to as a vinylidene fluoride polymer powder (c10).
  • Example 18 As the Henschel mixer, a product name FM10B / I manufactured by Mitsui Mining Co., Ltd. was used.
  • the temperature of the vinylidene fluoride polymer powder (6) itself reached 100 ° C. was raised to 110 ° C. over 2 minutes, further raised to 120 ° C. over 2 minutes, and further over 1 minute.
  • the temperature was raised to 125 ° C., further raised to 130 ° C. over 1 minute, further raised to 135 ° C. over 1 minute, and further raised to 140 ° C. over 1 minute.
  • Example 19 As the Henschel mixer, a product name FM10B / I manufactured by Mitsui Mining Co., Ltd. was used.
  • the temperature of the vinylidene fluoride polymer powder (6) itself reached 100 ° C. was raised to 110 ° C. over 2 minutes, further raised to 120 ° C. over 2 minutes, and further over 1 minute. The temperature was raised to 125 ° C. and further raised to 130 ° C. over 1 minute.
  • Example 20 As the Henschel mixer, a product name FM10B / I manufactured by Mitsui Mining Co., Ltd. was used.
  • the temperature of the vinylidene fluoride polymer powder (5) itself reached 100 ° C. was raised to 110 ° C. over 2 minutes, further raised to 120 ° C. over 2 minutes, and further over 1 minute. The temperature was raised to 125 ° C. and further raised to 130 ° C. over 1 minute. After reaching 130 ° C., the sample was held at 130 ° C. for 20 minutes and then sampling was performed. The obtained sample was allowed to cool at room temperature to obtain a heat-treated vinylidene fluoride polymer powder (20).
  • Example 21 As the Henschel mixer, a product name FM10B / I manufactured by Mitsui Mining Co., Ltd. was used.
  • the temperature was raised to 110 ° C. over 2 minutes from the time when the temperature of the vinylidene fluoride polymer powder (5) itself reached 100 ° C., and further raised to 120 ° C. over 2 minutes. After reaching 120 ° C., the sample was held at 120 ° C. for 20 minutes and then sampled. The obtained sample was allowed to cool at room temperature to obtain a heat-treated vinylidene fluoride polymer powder (21).
  • Example 22 As the Henschel mixer, a product name FM10B / I manufactured by Mitsui Mining Co., Ltd. was used.
  • the temperature was raised to 110 ° C. over 2 minutes from the time when the temperature of the vinylidene fluoride polymer powder (5) itself reached 100 ° C. After reaching 110 ° C., the sample was held at 110 ° C. for 20 minutes and then sampling was performed. The obtained sample was allowed to cool at room temperature to obtain a heat-treated vinylidene fluoride polymer powder (22).
  • the temperature of the vinylidene fluoride polymer powder itself is such that, when heat treatment is performed using a hot air circulating furnace, the vinylidene fluoride polymer powder in the kraft paper box Measured by inserting a thermocouple into the layer formed from Moreover, when heat processing was performed using a Henschel mixer, it measured by inserting a thermocouple in the vinylidene fluoride polymer powder inside a Henschel mixer.
  • Tables 1 to 8 show the results of Examples and Comparative Examples.

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WO2020054273A1 (ja) 2018-09-11 2020-03-19 株式会社クレハ フッ化ビニリデン系ポリマー粉末、バインダー組成物、電極合剤、および電極の製造方法
KR20210041115A (ko) 2018-09-11 2021-04-14 가부시끼가이샤 구레하 전극 합제, 전극 합제의 제조방법 및 전극의 제조방법

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CN113056504A (zh) * 2018-11-22 2021-06-29 索尔维特殊聚合物意大利有限公司 用于制造经热处理的pvdf的方法
CN110575760B (zh) * 2019-08-28 2021-11-02 安徽正旺膜分离技术股份有限公司 一种纤维增强型pvdf超滤膜的制备方法
CN110575761B (zh) * 2019-08-28 2021-09-10 北京汇智善水环境科技有限公司 一种纤维增强型pvdf超滤膜及其市政污水、工业废水中的应用
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WO2020054273A1 (ja) 2018-09-11 2020-03-19 株式会社クレハ フッ化ビニリデン系ポリマー粉末、バインダー組成物、電極合剤、および電極の製造方法
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KR20210041115A (ko) 2018-09-11 2021-04-14 가부시끼가이샤 구레하 전극 합제, 전극 합제의 제조방법 및 전극의 제조방법
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